Fibre-reactive dyes and dye mixtures and their use

ABSTRACT

The invention relates to dye mixtures which contain dyes of the formulae ##STR1## and to dyes of the formula ##STR2## in which A 1 , A 2 , A 3 , B, B 1 , R 1 , R 2 , R 3 , R 4 , R 5 , Z 1 , Z 2 , X 1 , X 2  and X 3  are as defined in claim 1. 
     The dyes and dye mixtures are distinguished by generally good properties and produce dyeings and prints having good wet and light fastness properties.

This is a continuation of Ser. No. 08/048,082, filed Apr. 15, 1993,abandoned, which is a division of Ser. No. 07/764,555, filed on Sep. 20,1991, now U.S. Pat. No. 5,232,462.

The present invention relates to fibre-reactive dyes and mixtures offibre-reactive dyes which are suitable for dyeing cellulose-containingfibre materials from an aqueous bath and for printingcellulose-containing fibre materials, which are suitable for dyeing bythe exhaust method and continuous method and produce wet fast and lightfast dyeings.

The invention relates to dye mixtures which contain dyes of the formulae##STR3## in which A₁, A₂ and A₃, independently of one another, are theradical of a monoazo, polyazo, metal complex azo, anthraquinone,phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene,triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone,pyrenequinone or perylenetetracarbimide dye, R₁, R₂, R₃, R₄ and R₅,independently of one another, are hydrogen or C₁ -C₄ alkyl, which can besubstituted by halogen, hydroxyl, cyano, C₁ -C₄ alkoxy, C₁ -C₄alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato, B is an aliphaticor aromatic bridging member, and Z₁ and Z₂ are hydrogen or an aliphatic,aromatic or heterocyclic radical, or Z₁ and Z₂, together with thenitrogen atom linking them, form a five- to seven-membered ring, whichapart from C atoms can contain further heteroatoms, and X₁, X₂ and X₃,independently of one another, are fluorine, chlorine, bromine, sulfo orcarboxypyridinium.

The invention also relates to dyes of the formula ##STR4## in which thesubstitutents A₂, A₃, R₂, R₃, R₄, R₅, X₂ and X₃ are as defined informula (2) and B₁ is an aliphatic bridging member.

The radical A₁, A₂ or A₃ can contain substituents customary for organicdyes bound to its basic structure.

Examples of further substituents in the radical A₁, A₂ or A₃ are: alkylgroups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl,isopropyl or butyl, alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups having1 to 8 carbon atoms, in particular alkanoylamino groups, such asacetylamino, propionylamino or benzoylamino, phenylamino,N,N-di-β-hydroxyethylamino, N,N-di-β-sulfatoethylamino,sulfobenzylamino, N,N-disulfobenzylamino, alkoxycarbonyl having 1 to 4carbon atoms in the alkoxy radical, such as methoxycarbonyl orethoxycarbonyl, alkylsulfonyl having 1 to 4 carbon atoms, such asmethylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen,such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoylhaving 1 to 4 carbon atoms in the alkyl radical, such asN-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfamoylhaving 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl,N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl,N-(β-hydroxyethyl)sulfamoyl, N,N-di-(β-hydroxyethyl)sulfamoyl,N-phenylsulfamoyl, ureido, hydroxyl, carboxyl, sulfomethyl or sulfo andfibre-reactive radicals. The radical A₁, A₂ or A₃ preferably containsone or more sulfo groups. Reactive dyes of the formulae (1) and (2), inwhich A₁, A₂ or A₃ is the radical of an azo dye, contain as substituentsin particular methyl, ethyl, methoxy, ethoxy, acetylamino, benzoylamino,amino, chlorine, bromine, ureido, hydroxyl, carboxyl, sulfomethyl orsulfo.

An alkyl radical R₁, R₂, R₃, R₄ or R₅ is straight-chain or branched; itcan be further substituted, for example by halogen, hydroxyl, cyano, C₁-C₄ alkoxy, C₁ -C₄ alkoxycarbonyl, carboxyl, sulfamoyl, sulfo orsulfato. Examples of suitable R₁, R₂, R₃, R₄ and R₅ radicals are asfollows: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, carboxymethyl, β-carboxyethyl, β-carboxypropyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl,β-ethoxyethyl, β-methoxypropyl, β-chloroethyl, γ-bromopropyl,β-hydroxyethyl, β-hydroxybutyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl,aminosulfonylmethyl and β-sulfatoethyl. R₁, R₂, R₃, R₄ and R₅,independently of one another, are preferably hydrogen, methyl or ethyl.

The radicals X₁, X₂ and X₃, independently of one another, are fluorine,chlorine, bromine, carboxypyridinium or a sulfo group. X₁, X₂ and X₃ arepreferably fluorine or chlorine.

The aliphatic or aromatic bridging member B is preferably an alkylene,aralkylene or arylene radical. The term aliphatic bridging member alsoincludes cycloaliphatic radicals. Thus, B can be a straight-chain orbranched C₁ -C₁₀ alkylene radical; it is in particular an alkyleneradical having 2 to 6 carbon atoms, for example ethylene, propylene,butylene, hexylene or cyclohexylene. Examples of an arylene radical Bare a naphthylene radical, the radical of a diphenyl or stilbene or inparticular a phenylene radical. An aralkylene radical B is in particulara benzylene radical. The radical B can contain further substituents, forexample halogen atoms, such as fluorine, chlorine and bromine, alkylgroups having 1 to 4 carbon atoms, such as methyl, ethyl and propyl,alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy,propoxy and isopropoxy, carboxyl or sulfo. B is preferably C₂ -C₆alkylene or substituted or unsubstituted phenylene. The ethyleneradical, phenylene radical and sulfophenylene radical are preferred.

The aliphatic bridging member B₁ is preferably an alkylene radical. Theterm aliphatic bridging member also includes cycloaliphatic radicals.Thus, B₁ can be a straight-chain or branched C₁ -C₁₀ alkylene radical;it is in particular an alkylene radical having 2 to 6 carbon atoms, forexample ethylene, propylene, butylene, hexylene or cyclohexylene. Theradical B₁ can contain further substituents, for example halogen atoms,such as fluorine, chlorine and bromine, alkyl groups having 1 to 4carbon atoms, such as methyl, ethyl and propyl, alkoxy groups having 1to 4 carbon atoms, such as methoxy, ethoxy, propoxy and isopropoxy,carboxyl or sulfo. B₁ is preferably C₂ -C₆ alkylene. The ethyleneradical is preferred.

Examples of suitable substituted amino groups ##STR5## are: alkylamino,N,N-dialkylamino, cycloalkylamino, N,N-dicycloalkylamino, aralkylamino,arylamino groups, differently substituted amino groups, such asN-alkyl-N-cyclohexylamino and N-alkyl-N-arylamino groups, furthermoreamino groups containing heterocyclic radicals, which may contain furtherfused-on carbocyclic rings, and amino groups in which the amino nitrogenatom is a member of an N-heterocyclic ring which may contain furtherhetero atoms. The abovementioned alkyl radicals can be straight-chain orbranched and can have a low or high molecular weight, alkyl radicalshaving 1 to 6 carbon atoms being preferred; suitable cycloalkyl, aralkyland aryl radicals are in particular cyclohexyl, benzyl, phenethyl,phenyl and naphthyl radicals; heterocyclic radicals are in particularfuran, thiophene, pyrazole, pyridine, pyrimidine, quinoline,benzimidazole, benzothiazole and benzoxazole radicals; amino groups inwhich the amino nitrogen atom is a member of an N-heterocyclic ring arepreferably radicals of six-membered N-heterocyclic compounds, which maycontain nitrogen, oxygen and sulfur as further heteroatoms. Theabovementioned alkyl, cycloalkyl, aralkyl and aryl radicals, theheterocyclic radicals and the N-heterocyclic rings can be furthersubstituted, for example by halogen, such as fluorine, chlorine andbromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ -C₄alkyl, C₁ -C₄ alkoxy, acylamino groups, such as acetylamino, ureido,hydroxyl, carboxyl, sulfomethyl and sulfo. The amino group ##STR6## canfurthermore contain fibre-reactive radicals.

Examples of the amino radical ##STR7## in formula (1) are: --NH₂,methylamino, ethylamino, propylamino, isopropylamino, butylamino,β-(acetylamino)ethylamino, hexylamino, β-methoxyethylamino,γ-methoxypropylamino, β-ethoxyethylamino, N,N-dimethylamino,N,N-diethylamino, β-chloroethylamino, β-cyanoethylamino,γ-cyanopropylamino, β-carboxyethylamino, sulfomethylamino,β-sulfoethylamino, β-hydroxyethylamino, N,N-di-β-hydroxyethylamino,γ-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino,N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-propyl-N-phenylamino,N-butyl-N-phenylamino, N-β-cyanoethyl-N-phenylamino,N-ethyl-2-methylphenylamino, N-ethyl-4-methylphenylamino,N-ethyl-3-sulfophenylamino, N-ethyl-4-sulfophenylamino, phenylamino,toluidino, xylidino, chloroanilino, anisidino, phenetidino, 2-, 3- and4-sulfoanilino, 2,5-disulfoanilino, sulfomethylanilino,N-sulfomethylanilino, 3- and 4-carboxyphenylamino,2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino,4-sulfo-(1)-naphthylamino, 3,6-disulfonaphthyl-(1)-amino,3,6,8-trisulfo-1-naphthylamino, 4,6,8-trisulfo-1-naphthylamino,6-sulfo-2-naphthylamino, 2-pyridylamino, morpholino, piperidino undpiperazino.

Other suitable reactive dyes of the formulae (1), (2) and (2a) are thosein which the radical A₁, A₂ or A₃ includes a further reactive radical.The additional reactive radicals included in A₁, A₂ or A₃ can be bound,for example to A₁, A₂ or A₃ by a direct bond, via amino groups or in adifferent manner.

An additional reactive radical included, if desired, in A₁, A₂ or A₃ orZ₁ or Z₂ is in particular a low-molecular-weight alkanoyl oralkylsulfonyl radical substituted by a detachable atom or a detachablegroup, a low-molecular-weight alkenoyl or alkenesulfonyl radical whichis unsubstituted or substituted by a detachable atom or a detachablegroup, a carbo- or heterocyclic radical containing 4-, 5- or 6-memberedrings, bound via a carbonyl or sulfonyl group and substituted by adetachable atom or a detachable group or a triazine or pyrimidineradical bound directly via a carbon atom and substituted by a detachableatom or a detachable group, or contains such a radical. Examples ofreactive radicals of this type are a six-membered heterocyclic radicalbound via an amino group and containing halogen atoms, such as ahalotriazine or halopyrimidine radical or an aliphatic acyl radical,such as an haloacetyl or halopropionyl radical.

Additional reactive radicals included in A₁, A₂, A₃, Z₁ and Z₂ are inparticular heterocyclic radicals containing at least one detachablesubstituent bound to a heterocyclic radical, inter alia those containingat least one reactive substituent bound to a 5- or 6-memberedheterocyclic ring, such as to a monoazine, diazine, triazine, forexample pyridine, pyrimidine, pridazine, pyrazine, thiazine, oxazine orasymmetrical or symmetrical, triazine ring or to such a ring systemwhich contains one or more fused-on aromatic rings, such as a quinoline,phthalazine, quinoline, quinazoline, quinoxaline, acridine, phenazineand phenanthridine ring system; the 5- or 6-membered heterocyclic ringscontaining at least one reactive substituent are thus preferably thosewhich contain one or more nitrogen atoms and can contain fused-on 5- orpreferably 6-membered carbocyclic rings.

Examples of reactive substituents on the heterocycle are: halogen (Cl,Br or F), ammonium, including hydrazinium and sulfonium, sulfonyl,azido(N₃), thiocyanato, mercapto, mercaptoether, hydroxyether, sulfinoand sulfo. Individual examples are:

Mono- or dihalo-symmetrical-triazinyl radicals, for example2,4-dichloro-6-triazinyl, 2-amino-4-chloro-6-triazinyl,2-alkylamino-4-chloro-6-triazinyl, such as2-methylamino-4-chloro-6-triazinyl, 2-ethylamino- or3-propylamino-4-chloro-6-triazinyl,2-β-hydroxyethylamino-4-chloro-6-triazinyl,2-di(β-hydroxyethyl)amino-4-chloro-6-triazinyl and the correspondingsulfuric monoesters, 2-diethylamino-4-chloro-6-triazinyl, 2-morpholino-or 2-piperidino-4-chloro-6-triazinyl,2-cyclohexylamino-4-chloro-6-triazinyl, 2-arylamino- and substitutedarylamino-4-chloro-6-triazinyl, such as2-phenylamino-4-chloro-6-triazinyl, 2-(o-, m- or p-carboxy- orsulfophenyl)amino-4-chloro-6-triazinyl, 2-alkoxy-4-chloro-6-triazinyl,such as 2-methoxy- or -ethoxy-4-chloro-6-triazinyl,2-(phenylsulfonylmethoxy)-4-chloro-6-triazinyl, 2-aryloxy- andsubstituted -aryloxy-4-chloro-6-triazinyl, such as2-phenoxy-4-chloro-6-triazinyl,2-(p-sulfophenyl)oxy-4-chloro-6-triazinyl, 2-(o-, m- or p-methyl- ormethoxyphenyl)oxy-4-chloro-6-triazinyl, 2-alkylmercapto- or2-arylmercapto- or 2-(substituted aryl)mercapto-4-chloro-6-triazinyl,such as 2-β-hydroxyethylmercapto-4-chloro-6-triazinyl,2-phenylmercapto-4-chloro-6-triazinyl,3-(4'-methyl)phenylmercapto-4-chloro-6-triazinyl,2-(2',4'-dinitro)phenylmercapto-4-chloro-6-triazinyl,2-methyl-4-chloro-6-triazinyl, 2-phenyl-4-chloro-6-triazinyl,2,4-difluoro-6-triazinyl, monofluorotriazinyl radicals substituted byamino, alkylamino, aralkylamino, acylamino groups of which alkyl, inparticular substituted or unsubstituted C₁ -C₄ alkyl, aralkyl, inparticular substituted or unsubstituted phenyl, C₁ -C₄ alkyl and aryl,in particular phenyl or naphthyl which ware unsubstituted or substitutedby sulfo, alkyl, in particular C₁ -C₄ alkyl, alkoxy, in particular C₁-C₄ alkoxy, carboxyl, acylamino groups and halogen atoms, such asfluorine, chlorine or bromine, for example 2-amino-4-fluoro-6-triazinyl,2-methylamino-4-fluoro-6-triazinyl, 2-ethylamino-4-fluoro-6-triazinyl,2-isopropylamino-4-fluoro-6-triazinyl,2-dimethylamino-4-fluoro-6-triazinyl,2-diethylamino-4-fluoro-6-triazinyl,2-β-methoxyethylamino-4-fluoro-6-triazinyl,2-β-hydroxyethylamino-4-fluoro-6-triazinyl,2-di(β-hydroxyethyl)amino-4-fluoro-6-triazinyl,2-β-sulfoethylamino-4-fluoro-6-triazinyl,2-β-sulfoethylmethylamino-4-fluoro-6-triazinyl,2-carboxymethylamino-4-fluoro-6-triazinyl,2-β-cyanoethylamino-4-fluoro-6-triazinyl,2-phenylamino-4-fluoro-6-triazinyl,2-β-phenylethylamino-4-fluoro-6-triazinyl,2-benzylmethylamino-4-fluoro-6-triazinyl, 2-(2'-, 3'- or4'-sulfobenzyl)amino-4-fluoro-6-triazinyl,2-cyclohexylamino-4-fluoro-6-triazinyl, 2-(o-, m-,p-methyl)phenylamino-4-fluoro-6-triazinyl, 2-(o-, m-,p-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2',5'-disulfo)phenylamino-4-fluoro-6-triazinyl, 2-(o-, m-,p-chloro)phenylamino-4-fluoro-6-triazinyl, 2-(o-, m-,p-methoxy)phenyl-4-fluoro-6-triazinyl,2-(2'-methyl-4'-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-methyl-5'-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-chloro-4'-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-chloro-5'-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-methoxy-4'-sulfophenyl)amino-4-fluoro-6-triazinyl, 2-(o-, m-,p-carboxy)phenylamino-4-fluoro-6-triazinyl,2-(2',4'-disulfo)-phenylamino-4-fluoro-6-triazinyl,2-(3',5'-disulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-carboxy-4-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(2'-carboxy-4-sulfo)phenylamino-4-fluoro-6-triazinyl,2-(6'-sulfo-2'-naphthylamino-4-fluoro-6-triazinyl,2-(4',8'-disulfo-2'-naphthyl)-amino-4-fluoro-6-triazinyl,2-(6',8'-disulfo-2'-naphthyl)-amino-4-fluoro-6-triazinyl,2-(N-methylphenyl)amino-4-fluoro-6-triazinyl,2-(N-ethylphenyl)amino-4-fluoro-6-triazinyl,2-(N-β-hydroxyethylphenyl)amino-4-fluoro-6-triazinyl,2-(N-isopropylphenyl)amino-4-fluoro-6-triazinyl,2-morpholino-4-fluoro-6-triazinyl, 2-piperidino-4-fluoro-6-triazinyl,2-(4',6',8'-trisulfo-2'-naphthyl)-4-fluoro-6-triazinyl,2-(3',6',8'-trisulfo-2'-naphthyl)-4-fluoro-6-triazinyl,2-(3',6'-disulfo-1-naphthyl)-4-fluoro-6-triazinyl, mono-, di- ortrihalopyrimidinyl radicals, such as 2,4-dichloro-6-pyrimidinyl,2,4,5-trichloro-6-pyrimidinyl, 2,4-dichloro-5-nitro- or -5-methyl- or-5-carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or-5-sulfo-or -5-mono-, -di- or-trichloromethyl- or -5-carboalkoxy-6-pyrimidinyl,2,6-dichloropyrimidine-4-carbonyl-, 2,4-dichloropyrimidine-5-carbonyl-,2-chloro-4-methylpyrimidine-5-carbonyl-,2-methyl-4-chloropyrimidine-5-carbonyl-,2-methylthio-4-fluoropyrimidine-5-carbonyl,6-methyl-2,4-dichloropyrimidine-5-carbonyl,2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl,2-chloroquinoxaline-3-carbonyl, 2- or3-monochloroquinoxaline-6-carbonyl, 2- or3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-6-carbonyl,2,3-dichloroquinoxaline-6-sulfonyl, 1,4-dichlorophthalazine-6-sulfonylor -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl,2- or 3- or 4-(4',5'-dichloropyridazin-6'-yl)phenylsulfonyl or-carbonyl, β-(4',5'-dichloro-1'-pyridazon-6'-yl)ethylcarbonyl,N-methyl-N-(2,4-dichloro-6-triazinyl)carbamyl,N-methyl-N-(2-methylamino-4-chloro-6-triazinyl)carbamyl,N-methyl-N-(2-dimethylamino-4-chloro-6-triazinyl)carbamyl, N-methyl- orN-ethyl-N-(2,4-dichloro-6-triazinyl)aminoacetyl,N-methyl-N-(2,3-dichloroquinoxaline-6-sulfonyl)aminoacetyl,N-methyl-N-(2,3-dichloroquinoxaline-6-carbonyl)aminoacetyl, and thecorresponding bromine and fluorine derivatives of the abovementionedchloro-substituted heterocyclic radicals, of these, for example,2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl,2,6-difluoro-5-chloro-4-pyrimidinyl,2-fluoro-5,6-dichloro-4-pyrimidinyl,2,6-difluoro-5-methyl-4-pyrimidinyl,2,5-difluoro-6-methyl-4-pyrimidinyl,2-fluoro-5-methyl-6-chloro-4-pyrimidinyl,2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl,2-fluoro-5-cyano-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl,2,5,6-trifluoro-4-pyrimidinyl,5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl,2,6-difluoro-5-bromo-4-pyrimidinyl,2-fluoro-5-bromo-6-methyl-4-pyrimidinyl,2-fluoro-5-bromo-6-chloromethyl-4-pyrimidinyl,2,6-difluoro-5-chloromethyl-4-pyrimidinyl,2,6-difluoro-5-nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl,2-fluoro-5-chloro-6-methyl-4-pyrimidinyl,2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro-6-chloro-4-pyrimidinyl,6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl,6-trifluoromethyl-2-fluoro-4-pyrimidinyl,2-fluoro-5-nitro-4-pyrimidinyl,2-fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carboxamido-4-pyrimidinyl,2-fluoro-5-carbomethoxy-4-pyrimidinyl,2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl,2-fluoro-6-carboxamido-4-pyrimidinyl,2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl-4-pyrimidinyl,2-fluoro-6-cyano-4-pyrimidinyl,2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl,2-fluoro-5-sulfonamido-4-pyrimidinyl,2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl,2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl,6-fluoro-5-chloro-4-pyrimidinyl,6-fluoro-5-trifluoromethyl-4-pyrimidinyl,6-fluoro-2-methyl-4-pyrimidinyl,6-fluoro-5-chloro-2-methyl-4-pyrimidinyl, 5,6-difluoro-4-pyrimidinyl,6-fluoro-5-chloro-2-trifluoromethyl-4-pyrimidinyl,6-fluoro-2-phenyl-4-pyrimidinyl, 6-fluoro-5-cyano-4-pyrimidinyl,6-fluoro-5-nitro-4-pyrimidinyl, 6-fluoro-5-methylsulfonyl-4-pyrimidinyl,6-fluoro-5-phenylsulfonyl-4-pyrimidinyl, sulfonyl-containing triazineradicals, such as 2,4-bis(phenylsulfonyl)-6-triazinyl,2-(3'-carboxyphenyl)sulfonyl-4-chloro-6-triazinyl,2-(3'-sulfophenyl)sulfonyl-4-chloro-6-triazinyl,2,4-bis(3'-carboxyphenylsulfonyl)-6-triazinyl; sulfonyl-containingpyrimidine rings, such as 2-carboxymethylsulfonyl-4-pyrimidinyl,2-methylsulfonyl-6-methyl-4-pyrimidinyl,2-methylsulfonyl-6-ethyl-4-pyrimidinyl,2-phenylsulfonyl-5-chloro-6-methylpyrimidinyl,2,6-bis(methylsulfonyl)-4-pyrimidinyl,2,6-bis(methylsulfonyl)-5-chloro-4-pyrimidinyl,2,4-bis(methylsulfonyl)pyrimidine-5-sulfonyl,2-methylsulfonyl-4-pyrimidinyl, 2-phenylsulfonyl-4-pyrimidinyl,2-trichloromethylsulfonyl-6-methyl-4-pyrimidinyl,2-methylsulfonyl-5-chloro-6-methyl-4-pyrimidinyl,2-methylsulfonyl-5-bromo-6-methyl-4-pyrimidinyl,2-methylsulfonyl-5-chloro-6-ethyl-4-pyrimidinyl,2-methylsulfonyl-5-chloro-6-chloromethyl-4-pyrimidinyl,2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl,2-methylsulfonyl-5-nitro-6-methyl-4-pyrimidinyl,2,5,6-tris(methylsulfonyl)-4-pyrimidinyl,2-methylsulfonyl-5,6-dimethyl-4-pyridinyl,2-ethylsulfonyl-5-chloro-6-methyl-4-pyrimidinyl,2-methylsulfonyl-6-chloro-4-pyrimidinyl,2,6-bis(methylsulfonyl)-5-chloro-4-pyrimidinyl,2-methylsulfonyl-6-carbonyl-4-pyrimidinyl,2-methylsulfonyl-5-sulfo-4-pyrimidinyl,2-methylsulfonyl-6-carbomethoxy-4-pyrimidinyl,2-methylsulfonyl-5-carboxy-4-pyrimidinyl,2-methylsulfonyl-5-cyano-6-methoxy-4-pyrimidinyl,2-methylsulfonyl-5-chloro-4-pyrimidinyl,2-sulfoethylsulfonyl-6-methyl-4-pyrimidinyl,2-methylsulfonyl-5-bromo-4-pyrimidinyl,2-phenylsulfonyl-5-chloro-4-pyrimidinyl,2-carboxymethylsulfonyl-5-chloro-6-methyl-4-pyrimidinyl,2-methylsulfonyl-6-chloropyrimidine-4- and -5-carbonyl,2,6-bis(methylsulfonyl)pyrimidine-4- or -5-carbonyl,2-ethylsulfonyl-6-chloropyrimidine-5-carbonyl,2,4-bis(methylsulfonyl)pyrimidine-5-sulfonyl,2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl or -carbonyl,ammonium-containing triazine rings, such as2-trimethylammonio-4-phenylamino- or -4-(o-, m- orp-sulfophenyl)amino-6-triazinyl,2-(1,1-dimethylhydrazinio)-4-phenylamino- or -4-(o-, m- orp-sulfophenyl)amino-6-triazinyl,2-(2-isopropylidene-1,1-dimethyl)hydrazinio-4-phenylamino- or-4-(o-, m-or p-sulfophenyl)amino-6-triazinyl, 2-N-aminopyrrolidinio- or2-aminopiperidinio-4-phenylamino- or-4-(o-, m- orp-sulfophenyl)amino-6-triazinyl, 2-N-aminopyrrolidinio- or2-N-aminopiperidinio-4-phenylamino- or-4-(o-, m- orp-sulfophenyl)amino-6-triazinyl, furthermore 4-phenylamino- or-4-(sulfophenylamino)-6-triazinyl radicals which contain1,4-diazabicyclo[2.2.2]octane or 1,2-diazabicyclo[0.3.3]octane boundquaternary in the 2 position via a nitrogen bond,2-pyridinio-4-phenylamino- or 4-(o-, m- orp-sulfophenyl)amino-6-triazinyl and the corresponding 2-onio-6-triazinylradicals which are substituted in the 4 position by alkylamino, such asmethylamino, ethylamino or β-hydroxyethylamino or alkoxy, such asmethoxy or alkoxy, or aroxy, such as phenoxy or sulfophenoxy groups:2-chlorobenzothiazole-5- or -6-carbonyl or -5- or -6-sulfonyl,2-arylsulfonyl- or alkylsulfonylbenzothiazole-5- or -6-carbonyl or -5-or -6-sulfonyl, such as 2-methylsulfonyl- or2-ethoxysulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl,2-phenylsulfonylbenzothiazole-5- or -6-sulfonyl or -carbonyl and thecorresponding 2-sulfonylbenzothiazole-5- or -6-carbonyl or -sulfonylderivatives containing sulfo groups in the fused-on benzene ring,2-chlorobenzoxazole-5- or -6-carbonyl or-sulfonyl,2-chlorobenzimidazole-5- or-6-carbonyl or -sulfonyl,2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl,2-chloro-4-methyl-1,3-thiazole-5-carbonyl or -4- or -5-sulfonyl, theN-oxide of 4-chloro- or 4-nitroquinoline-5-carbonyl or also the radicals5-chloro-2,6-difluoro-1,3-dicyanophenyl,2,4-difluoro-1,3,5-tricyanophenyl, 2,4,5-trifluoro-1,3-dicyanophenyl,2,4-dichloro-5-methylsulfonyl-6-pyrimidinyl,2,4-trichloro-5-ethylsulfonyl-6-pyrimidinyl,2-fluoro-5-methylsulfonyl-6'-(2'-sulfophenylamino)-4-pyrimidinyl,2,5-dichloro-6-methylsulfonyl-6-pyrimidinyl

Further reactive groups of the aliphatic series are acrylolyl, mono-,di- or trichloroacryloyl groups, such as --CO--CH═CH--Cl, --CO--CCl═CH₂,--CO--CCl═CH--CH₃, furthermore --CO--CCl═CH--COOH, --CO--CH═CCl--COOH,β-chloropropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl,2-fluoro-2-chloro-3,3-difluorocyclobutane-1-carbonyl,2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl,2,2,3,3-tetrafluorocyclobutane-1-aryloxy, α- or β-bromoacrylolyl, α- orβ-alkyl or -arylsulfoacrylolyl, such as α- or β-methylsulfonylacrylolyl,and chloroacetyl.

An example of a suitable aliphatic radical Z₁ or Z₂ in formula (1) is asubstituted or unsubstituted C₁ -C₈ alkyl radical or a substituted orunsubstituted C₅ -C₇ cycloalkyl radical.

Examples of Z₁ and Z₂ as C₁ -C₈ alkyl are methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl orn-octyl. The C₁ -C₈ alkyl radicals Z₁ and Z₂ can be substituted, forexample by halogen, hydroxyl, cyano, carboxyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoyl, hydroxy-C₂ -C₄ alkoxy, sulfo, sulfato, phenyl and naphthyl, itbeing possible for the phenyl or naphthyl radical to be furthersubstituted, for example as mentioned for A₁, A₂ or A₃. Examples are:β-carboxyethyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl, benzyl,phenethyl, β-acetylaminoethyl.

Suitable C₅ -C₇ cycloalkyl radicals for Z₁ and Z₂ are cyclopentyl,cyclohexyl or cycloheptyl radicals, which can be further substituted,for example by C₁ -C₄ alkyl. Examples are: cyclopentyl, cyclohexyl,4-methylcyclohexyl, and cycloheptyl.

Suitable aromatic radicals for Z₁ and Z₂ are in particular phenyl ornaphthyl and phenyl or naphthyl radicals substituted, for example, by C₁-C₄ alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, C₁-C₄ alkoxy, for example methoxy or ethoxy, halogen, for examplefluorine, chlorine or bromine, carboxyl, hydroxyl or sulfo.

Suitable heterocyclic radicals for Z₁ and Z₂ are in particular a furan,thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole,benzothiazole or benzoxazole radical, it being possible for the radicalsmentioned to be substituted by the substituents mentioned for A₁, A₂ orA₃.

In the case where Z₁ and Z₂, together with the nitrogen atom linkingthem, possibly with the inclusion of a further heteroatom, form anitrogen-containing heterocyclic ring examples are a piperidinyl,piperazinyl or morpholinyl radical.

Preferred dye mixtures of the reactive dyes of the formulae (1) and (2)are those in which

a) A₁, A₂, A₃, Z₁ and Z₂, independently of one another, containfibre-reactive radicals,

b) the weight ratio of the dyes of the formulae (1):(2) is 5:95 to 95:5,in particular 30:70 to 70:30,

c) B is --(CH₂)--₂₋₆, unsubstituted or C₁ -C₄ alkyl-substitutedcyclohexylene, unsubstituted or substituted phenylene or a radical ofthe formula ##STR8## in which the benzene ring I can contain furthersubstituents, in particular B is --(CH₂)--₂₋₆, preferably ethylene, or##STR9## d) the radical --N(Z₁)Z₂ is --NH₂, ##STR10## or --NH--(CH₂)₂--NH--CO--CH₃, e) X₁, X₂ and X₃, independently of one another, arefluorine or chlorine, in particular fluorine,

f) R₁, R₂, R₃, R₄ and R₅, independently of one another, are hydrogen,methyl or ethyl, R₃ and R₄ being in particular hydrogen,

g) A₁, A₂ and A₃, independently of one another, are monoazo or disazodye radicals, metal complex azo dye radicals or formazan dye radicals,

h) the radicals A₂ and A₃ are identical,

i) the radicals A₁, A₂ and A₃ are identical.

Preferred reactive dyes of the formula (2a) are those in which

a) A₂ and A₃, independently of one another contain fibre-reactiveradicals,

b) B₁ is --(CH₂)--₂₋₆, unsubstituted or C₁ -C₄ alkyl-substitutedcyclohexylene, in particular B₁ is --(CH₂)--₂₋₆, preferably ethylene,

c) X₂ and X₃, independently of one another, are fluorine or chlorine, inparticular fluorine,

d) R₂, R₃, R₄ and R₅, independently of one another, are hydrogen, methylor ethyl, R₃ and R₄ being in particular hydrogen,

e) A₂ and A₃, independently of one another, are monoazo or disazo dyeradicals, metal complex azo dye radicals, or formazan dye radicals,

f) the radicals A₂ and A₃ are identical.

Particularly preferred dye mixtures of the reactive dyes of the formulae(1) and (2) are those in which

a) X₁, X₂ and X₃ are fluorine,

b) R₃ and R₄ are each a hydrogen atom,

c) the benzene ring I is unsubstituted or substituted by sulfo,

d) A₂ has the same meaning as A₃ and R₂ the same meaning as R₅,

e) A₁, A₂ and A₃ are each an azo, metal complex azo or formazan dyeradical.

Of particular importance are dye mixtures of the reactive dyes of theformulae (1) and (2) or dyes of the formula (2a) in which A₁, A₂ and A₃,or A₂ and A₃ (in the case of the dyes of the formula (2a)) are each aradical of the formulae (3) to (15) below: ##STR11## in which R₆represents 0 to 3 substituents from the group comprising C₁ -C₄ alkyl,C₁ -C₄ alkoxy, halogen, carboxyl and sulfo. ##STR12## in which R₆represents 0 to 3 substituents from the group comprising C₁ -C₄ alkyl,C₁ -C₄ alkoxy, halogen, carboxyl and sulfo. ##STR13## in which R₆represents 0 to 3 substituents from the group comprising C₁ -C₄ alkyl,C₁ -C₄ alkoxy, halogen, carboxyl and sulfo. ##STR14## in which R₆represents 0 to 4 substituents from the group comprising halogen, nitro,cyano, trifluoromethyl, sulfamoyl, carbamoyl, C₁ -C₄ alkyl, C₁ -C₄alkoxy, amino, acetylamino, ureido, hydroxyl, carboxyl, sulfomethyl andsulfo independently of one another. ##STR15## in which R₈ is C₁ -C₄alkanoyl or benzoyl. ##STR16## in which R₈ is C₁ -C₄ alkanoyl orbenzoyl. ##STR17## in which R₉ represents 0 to 3 substituents from thegroup comprising C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl andsulfo. ##STR18## in which R₁₂ and R₁₀, independently of one another, arehydrogen, C₁ -C₄ alkyl or phenyl, and R₁₁ is hydrogen, cyano, carbamoylor sulfomethyl. ##STR19## in which R₉ represents 0 to 3 substituentsfrom the group comprising C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyland sulfo. ##STR20## in which R₁₃ represents 0 to 2 substituents fromthe group comprising C₁ -C₄ alkyl, C₁ -C₄ alkoxy, halogen, carboxyl andsulfo; and Z is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,β-acyloxyethyl, β-haloethyl or vinyl. ##STR21## in which R₁₄ represents0 to 2 substituents from the group comprising C₁ -C₄ alkyl, C₁ -C₄alkoxy, halogen, carboxyl and sulfo; and Z is β-sulfatoethyl,β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl orvinyl.

Furthermore, of particular importance are heavy metal complexes ofreactive dyes of the formula (1); suitable complexing heavy metals arein particular copper, nickel, cobalt or chromium. Preference is given tocopper complex azo dyes, in particular those of the formulae (3) to (13)which contain the copper atom bound in the ortho position relative tothe azo bridge via an oxygen atom.

Examples of azo dyes which are suitable as metal complexes are:##STR22##

Preferred metal atoms are Cu (1:1 complex) or Cr and Co (1:2 complex).Cr and Co complexes can contain the azo compound of the abovementionedformula once or twice, i.e. they can have a symmetrical or, togetherwith any desired other ligands, an unsymmetrical structure.

Preference is given to copper complexes, for example ##STR23##

In the formulae listed above, the radicals R₂₄ to R₂₆ are hydrogen or C₁-C₄ alkyl. The radicals R₂₄ to R₂₆ are preferably hydrogen, methyl orethyl. The aromatic rings in the above dyes can be further substituted,the benzene rings in particular by methyl, ethyl, methoxy, ethoxy,methylsulfonyl, ethylsulfonyl, carboxyl, acetylamino or chlorine, andthe naphthalene rings in particular by methoxy, carboxyl, acetylamino,nitro or chlorine. Preferably, the benzene rings are not furthersubstituted.

The reactive dyes of the formulae (1), (2) and (2a) are known per se orcan be prepared by reacting one or two equivalents of an organic dye ofthe formula ##STR24## or a dye precursor, at least one equivalent of ans-triazine, at least one equivalent of a diamine of the formula##STR25## or of the formula ##STR26## or one equivalent of an amine ofthe formula ##STR27## with one another in any desired order, A₁, A₂, A₃,R₁, R₂, R₃, R₄, R₅, B, B₁, Z₁ and Z₂ being as defined in formulae (1),(2) and (2a), or, in the case where dye precursors are used, conveningthe intermediates obtained into the desired dyes and, if desiredsubsequently carrying out a further conversion reaction.

The final dyes are prepared from the precursors in particular bycoupling reactions, which lead to azo dyes.

Since the individual abovementioned process steps can be carried out ina different order, if desired even simultaneously in some cases, variousprocess variants are possible. In general, the reaction is carried outin successive steps, the sequence of the simple reactions between theindividual reactants advantageously depending on the specificconditions.

Which of the possible process variants give the best results or underwhich specific conditions, for example at which condensationtemperature, it is most advantageous to carry out the reaction, dependson the structure of the starting materials. Since under certainconditions hydrolysis of a halotriazine radical takes place, anintermediate containing acetylamino groups has to be hydrolysed, inorder to remove the acetyl groups, before it is condensed with ahalotriazine. Which reaction, for example when a secondary condensationproduct is prepared from a compound of the formula (25), the triazineand the dye of the formula (24) or a precursor, is advantageouslycarried out first, the reaction of the triazine with the compound of theformula (25) or with the dye or a precursor of the dye, differs fromcase to case and depends in particular on the solubility of the aminocompounds involved and the basicity of the amino groups to be acylated.

Possible starting materials which can be used for preparing the reactivedyes of the formulae (1), (2) and (2a) are mentioned in detail below.##STR28##

Metal complexes of dyes of the formulae: ##STR29##

Preferred metal atoms are Cu (1:1 complex) or Cr and Co (1:2 complex).Cr and Co complexes can contain the azo compound of the abovementionedformula once or twice, i.e. they can have a symmetrical or, togetherwith any desired other ligands, an unsymmetrical structure. ##STR30##

In this formula, Pc is a Cu- or Ni-phthalocyanine radical, while thetotal number of substituents on the Pc structure is 4. ##STR31##

In the formulae listed above, the radicals R₁₇ to R₂₂ are hydrogen or C₁-C₄ alkyl, and the radicals R₁₅ and R₁₆ are hydrogen, C₁ -C₄ alkyl, C₁-C₄ alkoxy, C₁ -C₄ alkanoylamino, ureido or halogen, the radicals R₁₅and R₁₆, belonging to one and the same formula being independent of oneanother. The radicals R₁₇ to R₂₂ are preferably hydrogen, methyl orethyl, and the radicals R₁₅ and R₁₆ hydrogen, methyl, ethyl, methoxy,ethoxy, acetylamino, ureido or chlorine. The aromatic rings in the abovedyes can be further substituted, the benzene rings in particular bymethyl, ethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, carboxyl,acetylamino or chlorine, and the naphthaline rings in particular bymethoxy, carboxyl, acetylamino, nitro or chlorine; the same applies tothe anthraquinones, dioxazines, and the like. Preferably, the benzenerings are not further substituted.

Suitable triazines are:

2,4,6-Trifluoro-s-triazine (cyanuric fluoride),2,4,6-trichloro-s-triazine (cyanuric chloride),2,4,6-tribromo-s-triazine (cyanuric bromide), 2,4,6-trisulfo-s-triazine.

Diamines of formula (25)

4-Aminomethyl-3-sulfoaniline, 4-aminomethyl-2-sulfoaniline,1,2-diaminoethane, 1,3-diaminopropane, 1,2- or 1,3- or1,4-diaminobenzene.

Amines of the formula (26)

Ammonia, methylamine, dimethylamine, ethylamine, diethylamine,propylamine, isopropylamine, butylamine, dibutylamine, isobutylamine,sec-butylamine, tert-butylamine, hexylamine, methoxyethylamine,ethoxyethylamine, methoxypropylamine, chloroethylamine,hydroxyethylamine, dihydroxyethylamine, hydroxypropylamine,aminoethanesulfonic acid, β-(acetylamino)ethylamine,β-sulfatoethylamine, benzylamine, phenethylamine, cyclohexylamine,N-propylaminobenzene, N-isopropylaminobenzene, N-butylaminobenzene,N-isobutylaminobenzene, N-sec-butylaminobenzene, N-hexylaminobenzene,N-β-hydroxyethylaminobenzene, N-β-chloroethylaminobenzene,N-β-cyanoethylaminobenzene, N-β-sulfoethylaminobenzene,1-(N-ethylamino)-2-3- or -4-methylbenzene, 1-(N-ethylamino)-2-, -3-or-4-ethylbenzene, 1-(N-ethylamino)-2-, -3- or -4-chlorobenzene,1-N-ethylaminobenzene-3- or -4-sulfonic acid,1-(N-ethylamino)-4-butylbenzene, 1-(N-ethylamino)-4-hexylbenzene,1-(N-ethylamino)-4-octylbenzene, 1-(N-ethylamino)-4-vinylbenzene,1-N-n-butylamino-3-methylbenzene, 1-(N-ethylamino)-4-fluorobenzene,aniline, o-, m- and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and3,5-dimethylaniline, o-, m- and p-chloroaniline, N-methylaniline,N-ethylaniline, 3- or 4-acetylaminoaniline, 2,5-dimethoxyaniline, o-, m-and p-anisidine, o-, m- and p-phenetidine, 2-methoxy-5-methylaniline,2-ethoxy-5-methoxyaniline, 4-bromoaniline, 3-aminobenzamide,4-aminophenylsulfamide, 3-trifluoromethylaniline, 3- and4-aminophenylsulfamide, 3-trifluoromethylaniline, 3- and4-aminophenylurea, 1-naphthylamine, 2-naphthylamine, orthanilic acid,metanilic acid, sulfanilic acid, aniline-2,4-disulfonic acid,aniline-2,5-disulfonic acid, aniline-3,5-disulfonic acid, anthranilicacid, m- and p-aminobenzoic acid, 4-aminophenylmethanesulfonic acid,anilene-N-methanesulfonic acid, 2-aminotoluene-4-sulfonic acid,2-aminotoluene-5-sulfonic acid, p-aminosalicylic acid,1-amino-4-carboxybenzene-3-sulfonic acid,1-amino-2-carboxybenzene-5-sulfonic acid,1-amino-5-carboxybenzene-2-sulfonic acid, 1-naphthylamine-2-, -3-, -4-,-5-, -6-, -7- and -8-sulfonic acid, 2-naphthylamino-1-, -3-, -4-, -5-,-6-, -7- and -8-sulfonic acid, 1-naphthylamine-2,4-, -2,5-, -2,7-,-2,8-, -3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and-5,8-disulfonic acid, 2-naphthylamine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-,-4,7-, -4,8-, -5,7- and -6,8-disulfonic acid, 1-naphthylamine-2,4,6-,-2,4,7-, -2,5,7-, -3,5,7-, -3,6,8- and -4,6,8-trisulfonic acid,2-naphthylamine-1,3,7-, -1,5,7-, -3,5,7-, -3,6,7-, -3,6,8- and-4,6,8-trisulfonic acid, 2-, 3- and 4-aminopyridine,2-aminobenzothiazole, 5-, 6- and 8-aminoquinoline, 2-aminopyrimidine,morpholine, piperidine, piperazine.

The dye mixture according to the invention can be prepared by mixing theindividual dyes. This mixing process is carried out, for example, insuitable mills, for example ball and pinned disc mills, and in kneadersor mixers.

Furthermore, the dye mixtures can be prepared by spray drying theaqueous dye mixtures.

The invention furthermore relates to a process for the dyeing andprinting of cellulose-containing fibre materials using dye mixturescontaining the reactive dyes of the formulae (1) and (2) and using dyesof the formula (2a). Examples of suitable fibre materials are naturalcellulose fibres, such as cotton, linen and hemp, and cellulose andregenerated cellulose. The dye mixtures are also suitable for the dyeingor printing of hydroxyl-containing fibres present in blended fabrics,for example cotton blends with polyamide fibres or in particularpolyester fibres.

The dye mixtures according to the invention can be applied to the fibrematerial and fixed on the fibre in various ways, in particular in theform of aqueous dye solutions and printing pastes. They are suitable fordyeing not only by the exhaust method but also by the padding method, inwhich the material is impregnated with aqueous dye solutions which maycontain salts and the dyes are fixed after an alkali treatment or in thepresence of alkali, if desired with the application of heat. Afterfixing, the dyeings or prints are thoroughly rinsed with cold and hotwater, if desired with the addition of an agent acting as a dispersantand promoting the diffusion of the unfixed portions. For dyeing andprinting, the customary dyeing and printing processes are used.

The dye mixtures are distinguished by good fixation properties and verygood build-up properties. They can be used by the exhaust method over avery wide temperature range and are therefore also highly suitable fordyeing cotton/polyester blended fabrics under the conditions recommendedfor fabrics of this type. The degrees of fixation are high, and thedifference between the degree of exhaustion and the degree of fixationis remarkably small, i.e. the soaping loss is very low. The dye mixturesof the reactive dyes of the formulae (1) and (2), and the dyes of theformula (2a) are also suitable for printing, in particular on cotton,but also for printing nitrogen-containing fibres, for example wool orsilk or blended fabrics containing wool or silk.

The dyeings and prints on cellulose fibre materials produced using thedye mixtures according to the invention have a high colour strength anda high stability of the dye/fibre linkage, not only in the acidic butalso in the alkaline range, furthermore good light fastness and verygood wet fastness properties, such as wash, water, sea water,cross-dyeing and perspiration fastness properties, and good pleatingfastness, hot press fastness and rub fastness and very good chlorinatedwater fastness.

The dyes of the formulae (1), (2) and (2a) are present either in theform of their free sulfonic acid or preferably as salts thereof, forexample alkali metal salts, alkaline earth metal salts or ammonium saltsor as salts of an organic amine. Examples are the sodium salts, lithiumsalts or ammonium salts or the salt of triethanolamine.

The examples which follow serve to illustrate the invention. Thetemperatures are given in degrees centigrade, and parts and percentagesare by weight, unless stated otherwise. Parts by weight relate to partsby volume as the kilogram relates to the liter.

The preparation of the monoazo or disazo intermediates is not describedin the exemplary embodiments which follow, but it follows easily fromthe general description.

EXAMPLE 1

In order to prepare the dye mixtures containing a dye of the formula##STR32## and a dye of the formula (102), in a mixer ##STR33## a1) 40parts of the dye of the formula (101) and 60 parts of the dye of theformula (102) are mixed homogeneously in a mixer, to give 100 parts ofthe mixture designated below as dye mixture A;

a2) 5 parts of the dye of the formula (101) and 95 parts of the dye ofthe formula (102) are mixed homogeneously, to give 100 parts of themixture designated below as dye mixture A₂ ;

a3) 10 parts of the dye of the formula (101) and 90 parts of the dye ofthe formula (102) are mixed homogeneously, to give 100 parts of themixture designated below as dye mixture A₃ ;

in order to prepare the dye mixture containing the dye of the formula##STR34## and the dye of the formula (104), b) 20 parts of the dye ofthe formula (103) and 80 parts of the dye of the formula (104) are mixedhomogeneously;

in order to prepare the dye mixture containing the dye of the formula##STR35## and the dye of the formula (106), in a mixer c) 20 parts ofthe dye of the formula (105) and 80 parts of the dye of the formula(106) are homogeneously mixed;

in order to prepare the dye mixture containing the dye of the formula##STR36## and the dye of the formula ##STR37## in a mixer, d) 20 partsof the dye of the formula (107) and 80 parts of the dye of the formula(108) are homogeneously mixed, to give 100 parts of the mixturedesignated below as dye mixture D;

in order to prepare the dye mixture containing the dye of the formula##STR38## and the dye of the formula ##STR39## in a mixer, e) 20 partsof the dye of the formula (109) and 80 parts of the dye of the formula(110) are homogeneously mixed;

in order to prepare the dye mixture containing the dye of the formula##STR40## and the dye of the formula ##STR41## in a mixer, f) parts ofthe dye of the formula (111) and 70 parts of the dye of the formula(112) are homogeneously mixed, to give 100 parts of the mixturedesignated below as dye mixture F.

EXAMPLE 2

27.3 parts of the dye of the formula ##STR42## are dissolved in 600parts by volume of water and condensed with 7 parts of2,4,6-trifluoro-1,3,5-triazine. When no more diazotisable amino groupscan be detected, an aqueous solution containing 1.6 parts of2,4-diaminotoluene and 2,2 parts of morpholine are added to the dyesolution at 0° to 5° and a pH of 4.5. The pH of the reaction mixture isthen increased to 7.5 by addition of sodium carbonate and thetemperature is slowly raised to 25°. After condensation is complete, amixture of the dyes of the formulae ##STR43## is, after adding buffersalts, precipitated using sodium chloride, filtered, washed and dried.It is an orange powder and dyes cotton in golden yellow shades.

EXAMPLE 3

27.3 parts of the dye of the formula ##STR44## are dissolved in 600parts by volume of water and condensed with 7 parts of2,4,6-trifluoro-1,3,5-triazine. When no more diazotisable amino groupscan be detected, 0.75 part of ethylenediamine and 2,2 parts ofmorpholine are added to the dye solution at 0° to 5° and a pH of 5-7.The pH of the reaction mixture is then increased to 7.5 by addition ofsodium carbonate and the temperature is slowly raised to 25°. Aftercondensation is complete, a mixture of the dyes of the formulae##STR45## is, after adding buffer salts, precipitated using sodiumchloride, filtered, washed and dried. It is an orange powder and dyescotton in golden yellow shades.

The example is repeated, using 5.8 parts of metanilic acid, 2.7 parts ofo-toluidine, 2.7 parts of N-methylaniline or 3.0 parts of N-ethylanilineinstead of 2.2 parts of morpholine, to give mixtures of the dye of theformula ##STR46## with one of the dyes of the following formulae##STR47##

Depending on the molar ratios of the amines or diamines used, dyemixtures having different mixing ratios are obtained.

For example, the following diamines can be used instead ofethylenediamine: 1,3-propylenediamine, 1,2-propylenediamine,n-butylenediamine, 1-methyl-n-propylenediamine, n-hexylenediamine,2-ethyl-n-butylenediamine, 2-hydroxy-n-propylenediamine,1,3-diaminobenzene, 1,4-diaminobenzene, 1,3-diamino-4-chlorobenzene,1,3-diamino-4-methylbenzene, 1,3-diamino-4-ethylbenzene,1,3-diamino-4-methoxybenzene, 1,3-diamino-4-ethoxybenzene,1,4-diamino-2-methylbenzene, 1,4-diamino-2-methoxybenzene,1,4-diamino-2-ethoxybenzene, 1,4-diamino-2-chlorobenzene,1,4-diamino-2,5-dimethylbenzene, 1,4-diamino-2,5-diethylbenzene,1,4-diamino-2-methyl-5-methoxybenzene, 1,4-diamino-2,5-dimethoxybenzene,1,4-diamino-2,5-diethoxybenzene, 2,6-diamino-naphthalene,1,3-diamino-2,4,6-trimethylbenzene,1,4-diamino-2,3,5,6-tetramethylbenzene, 1,3-diamino-4-nitrobenzene,4,4'-diaminostilbene, 4,4'-diaminodiphenylmethane, 4,4'-diaminobiphenyl(benzidine), 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine,3,3'-dichlorobenzidine, 3,3'-dicarboxybenzidine,3,3'-dicarboxymethoxybenzidine, 2,2'-dimethylbenzidine,4,2'-diaminodiphenyl (diphenylene),2,6-diaminonaphthalene-4,8-disulfonic acid,1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5-disulfonicacid, 1,4-diaminobenzene-2,6-disulfonic acid,1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonicacid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid,1,4-diamino-2-methylbenzene-5-sulfonic acid,1,5-diamino-6-methylbenzene-3-sulfonic acid,1,3-diamino-6-methylbenzene-4-sulfonic acid, 3-(3'- or4'-aminobenzoylamino)-1-aminobenzene-6-sulfonic acid,1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulfonic acid,1,4-diaminobenzene-2-carboxylic acid, 1,3-diaminobenzene-4-carboxylicacid, 1,2-diaminobenzene-4-carboxylic acid,1,3-diaminobenzene-5-carboxylic acid, 1,4-diamino-2-methylbenzene,4,4'-diaminodiphenyloxide, 4,4'-diaminodiphenylurea-2,2'-disulfonicacid, 4,4'-diaminodiphenyloxyethane-2,2'-disulfonic acid,4,4'-diaminostilbene-2,2'-disulfonic acid,4,4'-diaminodiphenylethane-2,2'-disulfonic acid, piperazine.

The procedure as described in the examples is repeated, using thechromophores listed in column I of the table below instead of theabovementioned chromophore, to give further dye mixtures dyeing cottonin the shades given in column II.

    __________________________________________________________________________    I                                              II                             __________________________________________________________________________     ##STR48##                                     scarlet                         ##STR49##                                     red                             ##STR50##                                     red                             ##STR51##                                     blue                            ##STR52##                                     scarlet                         ##STR53##                                     greenish yellow                 ##STR54##                                     greenish yellow                 ##STR55##                                     yellow                          ##STR56##                                     yellow                          ##STR57##                                     scarlet                         ##STR58##                                     orange                          ##STR59##                                     bluish red                      ##STR60##                                     blue                            ##STR61##                                     brown                           ##STR62##                                     yellow                          ##STR63##                                     bluish red                      ##STR64##                                     dark blue                       ##STR65##                                     greenish navy                   ##STR66##                                     greenish blue                   ##STR67##                                     violet                          ##STR68##                                     blue                            ##STR69##                                     reddish blue                    ##STR70##                                     blue                            ##STR71##                                     greenish blue                   ##STR72##                                     cobalt blue                     ##STR73##                                     yellow                          ##STR74##                                     bluish red                      ##STR75##                                     bluish red                      ##STR76##                                     bluish red                      ##STR77##                                     turquoise                       ##STR78##                                     turquoise                       ##STR79##                                     red                             ##STR80##                                     yellow                          ##STR81##                                     yellow                          ##STR82##                                     blue                            ##STR83##                                     yellow                          ##STR84##                                     yellow                          ##STR85##                                     blue                            ##STR86##                                     bluish red                      ##STR87##                                     yellow                         __________________________________________________________________________

EXAMPLE 4

27.3 parts of the dye of the formula ##STR88## are dissolved in 600parts by volume of water and condensed with 7 parts of2,4,6-trifluoro-1,3,5-triazine. When no more diazotisable amino groupscan be detected, 2 to 2.5 parts of ethylenediamine are added to the dyesolution at 0° to 5° and a pH of 5-7. The pH of the reaction mixture isthen increased to 7.5 by adding sodium carbonate and the temperature isslowly raised to 25°. After condensation is complete, acylation iscarried out using 2 to 5 parts of acetic anhydride at a pH of 8-9. Amixture of the dyes of the formulae ##STR89## is then, after addingbuffer salts, precipitated using sodium chloride, filtered, washed anddried. It is an orange powder and dyes cotton in golden yellow shades.

Other acylating agents, in particular aliphatic, aromatic orheterocyclic carbonyl chlorides can be used instead of acetic anhydride,for example acetyl chloride, propionyl chloride, propionic anhydride,2-propanecarbonyl chloride, carboxypropionyl chloride, butyryl chloride,benzoyl chloride, 4-methylbenzoyl chloride, benzylcarbonyl chloride,4-sulfobenzylcarbonyl chloride and pyridine-3-carbonyl chloride.

The diamines or chromophores listed following Example 2 can also be usedinstead of the ethylenediamine and the chromophore mentioned.

EXAMPLE 5

2 parts of the dye mixtures A₁, A₂ or A₃ obtained according to Examples1a₁, 1a₂ or 1a₃ are dissolved in 400 parts of water; 1500 parts of asolution containing 53 g of sodium chloride per liter are added to thissolution. This dye bath is entered at 40° C. with 100 parts of a cottonfabric. After 45 minutes, 100 parts of a solution containing 16 g ofsodium hydroxide and 20 g of anhydrous Na₂ CO₃ per liter are added. Thetemperature of the dye bath is maintained at 40° C. for another 45minutes. The material dyed golden yellow is then rinsed, soaped at theboil for a quarter of an hour using a nonionic detergent, rinsed againand dried. The material obtained is distinguished by very good fastnessproperties, in particular wet fastness properties. The material obtainedhas very high colour strength.

EXAMPLE 6

2 parts of the dye mixture D obtained according to Example 1d aredissolved in 400 parts of water, 1500 parts of a solution containing 53g of sodium chloride per liter are added to this solution. This dye bathis entered at 35° C. with 100 parts of a cotton fabric. After 20minutes, 100 parts of a solution containing 16 g of sodium hydroxide and20 g of anhydrous Na₂ CO₃ per liter are added. The temperature of thedye bath is maintained at 35° C. for another 15 minutes. The temperatureis then increased to 60° C. over a period of 20 minutes. The temperatureis maintained at 60° C. for another 35 minutes. The material dyed orangeis then rinsed, soaped at the boil for a quarter of an hour using anonionic detergent, rinsed again and dried. The material obtained isdistinguished by very good fastness properties, in particular wetfastness properties. The material obtained has very high colourstrength.

EXAMPLE 7

8 parts of the dye mixture F obtained according to Example 1f aredissolved in 400 parts of water, 1400 parts of a solution containing 100g of sodium sulfate per liter are added to this solution. This dye bathis entered at 25° C. with 100 parts of a cotton fabric. After 10minutes, 200 parts of a solution containing 150 g of trisodium phosphateper liter are added. The temperature is then increased to 60° C. over aperiod of 10 minutes. The temperature is maintained at 60° C. foranother 90 minutes. The material dyed blue is then rinsed, soaped at theboil for a quarter of an hour using a nonionic detergent, rinsed againand dried. The material obtained is distinguished by very good fastnessproperties, in particular wet fastness properties. The material obtainedhas very high colour strength.

EXAMPLE 8

4 parts of the dye mixtures A₁, A₂ or A₃ obtained according to Examples1a₁, 1a₂ or 1a₃ are dissolved in 50 parts of water. 50 parts of asolution containing 5 g of sodium hydroxide and 20 g of anhydrous Na₂CO₃ per liter are added to the solution. The solution obtained is usedto pad a cotton fabric such that its liquor pickup is 70%, and thefabric is then wound onto a roller. It is left in this manner at roomtemperature for 3 hours. The material dyed golden yellow is then rinsed,soaped at the boil for a quarter of an hour using a nonionic detergent,rinsed again and dried. The material obtained is distinguished by verygood fastness properties, in particular wet fastness properties. Thematerial obtained has very high colour strength.

EXAMPLE 9

6 parts of the dye mixture D obtained according to Example 1 d aredissolved in 50 parts of water. 50 parts of a solution containing 16 gof sodium hydroxide per liter and 0.04 liter of water glass (38° Be) areadded to the solution. The solution obtained is used to pad a cottonfabric such that its liquor pickup is 70%, and the fabric is then woundonto a roller. It is left in this manner at room temperature for 10hours. The material dyed orange is then rinsed, soaped at the boil for aquarter of an hour using a nonionic detergent, rinsed again and dried.The material obtained is distinguished by very good fastness properties,in particular wet fastness properties. The material obtained has veryhigh colour strength.

EXAMPLE 10

2 parts of the dye mixture F obtained according to Example 1f aredissolved in 100 parts of water with the addition of 0.5 part of sodiumm-nitrobenzenesulfonate. The solution obtained is used to impregnate acotton fabric such that its liquor pickup is 75%, and the fabric is thendried. It is then impregnated with a warm solution of 20° C. containing4 g of sodium hydroxide and 300 g of sodium chloride per liter, squeezedoff to a liquor pickup of 75%, the blue dyeing is then steamed at 100°to 102° C. for 30 seconds, soaped in a 0.3% boiling solution of anonionic detergent for a quarter of an hour, rinsed and dried. Thematerial obtained is distinguished by very good fastness properties, inparticular wet fastness properties. The material obtained has very highcolour strength.

EXAMPLE 11

3 parts of the dye mixtures A₁, A₂ or A₃ obtained according to Examples1a₁, 1a₂ or 1a₃ are sprinkled into 100 parts of a stock thickenercontaining 50 parts of 5% sodium alginate thickener, 27.8 parts ofwater, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and1.2 parts of sodium bicarbonate with rapid stirring. The printing pastethus obtained is used to print a cotton fabric, and the printed fabricobtained is dried and steamed at 102° C. in saturated steam for 2minutes. The fabric printed golden yellow is then rinsed, if necessarysoaped at the boil, and rinsed again and then dried. The materialobtained is distinguished by very good fastness properties, inparticular wet fastness properties. The material obtained has very highcolour strength.

EXAMPLE 12

5 parts of the dye mixture D obtained according to Example 1d aresprinkled into 100 parts of a stock thickener containing 50 parts of 5%sodium alginate thickener, 36.5 parts of water, 10 parts of urea, 1 partof sodium m-nitrobenzenesulfonate and 2.5 parts of sodium bicarbonatewith rapid stirring. The printing paste thus obtained, whose stabilitymeets the technical requirements, is used to print a cotton fabric, andthe printed fabric obtained is dried and steamed at 102° C. in saturatedsteam for 8 minutes. The fabric printed orange is then rinsed, ifnecessary soaped at the boil, and rinsed again and then dried. Thematerial obtained is distinguished by very good fastness properties, inparticular wet fastness properties. The material obtained has very highcolour strength.

What is claimed is:
 1. A dye of the formula ##STR90## in which A₂ andA₃, independently of one another, are the radical of a monoazo dye ofthe formula ##STR91## in which R₁₂ and R₁₀, independently of oneanother, are hydrogen, C₁ -C₄ alkyl or phenyl, and R₁₁ is hydrogen,cyano, carbamoyl or sulfomethyl, or ##STR92## in which R₁₃ represents 0to 2 substituents selected from the group consisting of C₁ -C₄ alkyl, C₁-C₄ alkoxy, halogen, carboxyl and sulfo, and Z is β-sulfatoethyl,β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl orvinyl, R₂, R₃, R₄ and R₅, independently of one another, are hydrogen orC₁ -C₄ alkyl, B₁ is straight chain or branched C₁ -C₁₀ alkylene orunsubstituted or C₁ -C₄ alkyl-substituted cyclohexylene and X₂ and X₃are each fluorine.
 2. A dye according to claim 1, wherein R₂, R₃, R₄ andR₅ are hydrogen.
 3. A dye according to claim 1 wherein the radicals A₂and A₃ are identical.
 4. A dye according to claim 1 wherein A₂ and A₃are each a radical of the formula ##STR93## in which R₁₃ represents 0 to2 substituents from the group consisting of C₁ -C₄ alkyl, C₁ -C₄ alkoxy,halogen, carboxyl and sulfo, and Z is β-sulfatoethyl,β-thiosulfatoethyl, β-phosphatoethyl, β-acyloxyethyl, β-haloethyl orvinyl.
 5. A dye according to claim 1 wherein A₂ and A₃ are each aradical of the formula ##STR94## and B₁ is ethylene, 1,2- or1,3-propylene, n-butylene, 1-methyl-n-propylene, n-hexylene or2-ethyl-n-butylene.
 6. A dye according to claim 1 wherein A₂ and A₃ areeach a radical of the formula ##STR95## in which R₁₂ and R₁₀,independently of one another, are hydrogen, C₁ -C₄ alkyl or phenyl, andR₁₁ is hydrogen, cyano, carbamoyl or sulfomethyl, and B₁ is ethylene,1,2- or 1,3-propylene, n-butylene, 1-methyl-n-propylene, n-hexylene or2-ethyl-n-butylene.
 7. A process for the dyeing or printing ofcellulose-containing fibre materials by applying thereto a tinctoriallyeffective amount of a dye according to claim 1.